Enrique Burzurí

Kondo Effect in a Neutral and Stable All Organic Radical Single Molecule Break Junction

Organic radicals are neutral, purely organic molecules exhibiting an intrinsic magnetic moment due to the presence of an unpaired electron in the molecule in its ground state. This property, added to the low spin-orbit coupling and weak hyperfine interactions, make neutral organic radicals good candidates for molecular spintronics insofar as the radical character is stable in solid state electronic devices. Here we show that the paramagnetism of the polychlorotriphenylmethyl radical molecule in the form of a Kondo anomaly is preserved in two- and three-terminal solid-state devices, regardless of mechanical and electrostatic changes. Indeed, our results demonstrate that the Kondo anomaly is robust under electrodes displacement and changes of the electrostatic environment, pointing to a localized orbital in the radical as the source of magnetism. Strong support to this picture is provided by density functional calculations and measurements of the corresponding nonradical species. These results pave the way toward the use of all-organic neutral radical molecules in spintronics devices and open the door to further investigations into Kondo physics.

Franck–Condon Blockade in a Single-Molecule Transistor

We investigate vibron-assisted electron transport in single-molecule transistors containing an individual Fe4 Single-Molecule Magnet. We observe a strong suppression of the tunneling current at low bias in combination with vibron-assisted excitations. The observed features are explained by a strong electron-vibron coupling in the framework of the Franck-Condon model supported by density-functional theory.

Fabrication of hybrid molecular devices using multi-layer graphene break junctions

We report on the fabrication of hybrid molecular devices employing multi-layer graphene (MLG) flakes which are patterned with a constriction using a helium ion microscope or an oxygen plasma etch. The patterning step allows for the localization of a few-nanometer gap, created by electroburning, that can host single molecules or molecular ensembles. By controlling the width of the sculpted constriction, we regulate the critical power at which the electroburning process begins. We estimate the flake temperature given the critical power and find that at low powers it is possible to electroburn MLG with superconducting contacts in close proximity. Finally, we demonstrate the fabrication of hybrid devices with superconducting contacts and anthracene-functionalized copper curcuminoid molecules. This method is extendable to spintronic devices with ferromagnetic contacts and a first step towards molecular integrated circuits.

Exchange Coupling Inversion in a High-Spin Organic Triradical Molecule

The magnetic properties of a nanoscale system are inextricably linked to its local environment. In adatoms on surfaces and inorganic layered structures, the exchange interactions result from the relative lattice positions, layer thicknesses, and other environmental parameters. Here, we report on a sample-dependent sign inversion of the magnetic exchange coupling between the three unpaired spins of an organic triradical molecule embedded in a three-terminal device. This ferro-to-antiferromagnetic transition is due to structural distortions and results in a high-to-low spin ground-state change in a molecule traditionally considered to be a robust high-spin quartet. Moreover, the flexibility of the molecule yields an in situ electric tunability of the exchange coupling via the gate electrode. These findings open a route to the controlled reversal of the magnetic states in organic molecule-based nanodevices by mechanical means, electrical gating, or chemical tailoring.

Observing magnetic anisotropy in electronic transport through individual single-molecule magnets

We review different electron transport methods to probe the magnetic properties, such as the magnetic anisotropy, of an individual Fe4 SMM. The different approaches comprise first and higher order transport through the molecule. Gate spectroscopy, focusing on the charge degeneracy-point, is presented as a robust technique to quantify the longitudinal magnetic anisotropy of the SMM in different redox states. We provide statistics showing the robustness and reproducibility of the different methods. In addition, conductance measurements typically show high-energy excited states well beyond the ground spin multiplet of SMM. Some of these excitations have their origin in excited spin multiplets, others in vibrational modes of the molecule. The interplay between vibrations, charge and spin may yield a new approach for spin control.

Probing transverse magnetic anisotropy by electronic transport through a single-molecule magnet

By means of electronic transport, we study the transverse magnetic anisotropy of an individual Fe4 singlemolecule magnet (SMM) embedded in a three-terminal junction. In particular, we determine in situ the transverse anisotropy of the molecule from the pronounced intensity modulations of the linear conductance, which are observed as a function of applied magnetic field. The proposed technique works at temperatures exceeding the energy scale of the tunnel splittings of the SMM. We deduce that the transverse anisotropy for a single Fe4 molecule captured in a junction is substantially larger than the bulk value.

Transport mirages in single-molecule devices

Molecular systems can exhibit a complex, chemically tailorable inner structure which allows for targeting of specific mechanical, electronic, and optical properties. At the single-molecule level, two major complementary ways to explore these properties are molecular quantum-dot structures and scanning probes. This article outlines comprehensive principles of electron-transport spectroscopy relevant to both these approaches and presents a new, high-resolution experiment on a high-spin single-molecule junction exemplifying these principles. Such spectroscopy plays a key role in further advancing our understanding of molecular and atomic systems, in particular, the relaxation of their spin. In this joint experimental and theoretical analysis, particular focus is put on the crossover between the resonant regime [single-electron tunneling] and the off-resonant regime [inelastic electron (co)tunneling spectroscopy (IETS)]. We show that the interplay of these two processes leads to unexpected mirages of resonances not captured by either of the two pictures alone. Although this turns out to be important in a large fraction of the possible regimes of level positions and bias voltages, it has been given little attention in molecular transport studies. Combined with nonequilibrium IETS— four-electron pump-probe excitations—these mirages provide crucial information on the relaxation of spin excitations. Our encompassing physical picture is supported by a master-equation approach that goes beyond weak coupling. The present work encourages the development of a broader connection between the fields of molecular quantum-dot and scanning probe spectroscopy.

Electron-vibron coupling effects on electron transport via a single-molecule magnet

We investigate how the electron-vibron coupling influences electron transport via an anisotropic magnetic molecule, such as a single-molecule magnet (SMM) Fe4, by using a model Hamiltonian with parameter values obtained from density-functional theory (DFT). The magnetic anisotropy parameters, vibrational energies, and electron-vibron coupling strengths of the Fe4 are computed using DFT. A giant spin model is applied to the Fe4 with only two charge states, specifically a neutral state with a total spin S=5 and a singly charged state with S=9/2, which is consistent with our DFT result and experiments on Fe4 single-molecule transistors. In sequential electron tunneling, we find that the magnetic anisotropy gives rise to new features in the conductance peaks arising from vibrational excitations. In particular, the peak height shows a strong, unusual dependence on the direction as well as magnitude of applied B field. The magnetic anisotropy also introduces vibrational satellite peaks whose position and height are modified with the direction and magnitude of applied B field. Furthermore, when multiple vibrational modes with considerable electron-vibron coupling have energies close to one another, a low-bias current is suppressed, independently of gate voltage and applied B field, although that is not the case for a single mode with a similar electron-vibron coupling. In the former case, the conductance peaks reveal a stronger B-field dependence than in the latter case. The new features appear because the magnetic anisotropy barrier is of the same order of magnitude as the energies of vibrational modes with significant electron-vibron coupling. Our findings clearly show the interesting interplay between magnetic anisotropy and electron-vibron coupling in electron transport via the Fe4. Similar behavior can be observed in transport via other anisotropic magnetic molecules.

Redox-Induced Gating of the Exchange Interactions in a Single Organic Diradical

Embedding a magnetic electroactive molecule in a three-terminal junction allows for the fast and local electric field control of magnetic properties desirable in spintronic devices and quantum gates. Here, we provide an example of this control through the reversible and stable charging of a single all-organic neutral diradical molecule. By means of inelastic electron tunnel spectroscopy we show that the added electron occupies a molecular orbital distinct from those containing the two radical electrons, forming a spin system with three antiferromagnetically coupled spins. Changing the redox state of the molecule therefore switches on and off a parallel exchange path between the two radical spins through the added electron. This electrically controlled gating of the intramolecular magnetic interactions constitutes an essential ingredient of a single-molecule quantum gate.

Superconducting molybdenum-rhenium electrodes for single-molecule transport studies

We demonstrate that electronic transport through single molecules or molecular ensembles, commonly based on gold (Au) electrodes, can be extended to superconducting electrodes by combining gold with molybdenum-rhenium (MoRe). This combination induces proximity-effect superconductivity in the gold to temperatures of at least 4.6K and magnetic fields of 6 T, improving on previously reported aluminum based superconducting nanojunctions. As a proof of concept, we show three-terminal superconductive transport measurements through an individual Fe4 singlemolecule magnet.